Parasiticide



Paten f u 1.943

UNl'lED STATES, PATENT-{OF PARASITICIDE Ewald Urbscliat and F knsen I. G.-Werk,

rang Heckmanns, Lever- Germany, assignors to Winthrop Chemical Company, Inc., New York, I N. Y., a corporation of New York 1 No Drawing. Application April 6, 1940, Serial No. 328,376. In Germany- March 16,1939

scum. (cum-2st I R denotes an organic residue which is linked with one carbon atom to the nitrogen atom, R1

stands for a hydrogen atom or an organic residue and x stands either for R or the radical iLHiN R B. may, for instance, denote an alkyl radical including cycloalkyl and aralkyl radicals, or an aryl or a heterocyclic radical. It may, for instance, stand for methyl, ethyl, n-propyl, isopropyl, n-butyl, n-dodecyl, cyclohexyl or benzyl radicals. The said radicals mayalso be substituted, such as in the case of hydroxyalkyl or alkoxyalkyl radicals. R. may stand for the same or different radicals. If two radicals R are bo'lmd to one nitrogen atom' they may form a heterocyclic ring system. In the-above formula the roup.

N v R/ may be, for instance, a piperidyl or morpholyl residue OKs-CH: CHI-CHI c N- or o CHr-C I CHr-Cfii 8 wmN-cm-s-ti-mom 2,325,720 FI'CE fusicladium, wood-fungi, mold fungi.

larly aphides.

wherein X and Y stand for hydrogen, alkyl or aralkyl and Z stands for alkyl, aryl or the respectively, n being the integer 1, 2 or 3, they are distinguished by a much wider field of application. The lauryl-diethybdithiocarbamate, the most favored compound of the group of the known dithiocarbamic acid esters of the foregoing formula has hardly any action upon aphides. The known compounds are also practically unfit for seed dressing. For instance a dry seed dressing containing 2 per cent of tetramethylthiuramsulfide, when used in the usual proportion, has hardly any effect. The tetraalkylthiuram sulfides are effective only for combating fungus pests in orchards. My new compounds of the formula R s R1 R N- s-JJHN are, however, effective fungicides. They are, for

instance, suitable for combating, for instance, Further certain representatives of this group, for instance the compound of the probable formula CnHzs CrzHu N-CHzSfi-N\ CH3 CH3 may be used for exterminating insects, particu- Other compounds, such as the compound of the probable formula CHaN As contrasted to the benzene.

The said compounds may be prepared by several methods. The products of the general formula may, for instance, be obtained by reaction of 1 mol of the intermediate product-obtained by reacting 1 mol-oi an amine with, 1 mol-of an aldehyde-upon 1 mol of a dithiocarbamic acid. The reaction proceeds probably according to the following scheme:

- Inithis reaction the dithiocarbamic acid may be replaced by the starting compounds for its formation, 1. e. by a mixture containing an amine and Another method of preparing these products consists in the addition of an amine-hydrohalide to a metal salt of dithiocarbamic acid, preferably a watersoluble metal salt, in' the presence of an aldehyde. The reaction may be illustrated by the following probable reaction scheme:

mediate product-obtainable by reacting 1 mol of a primary amine and two mols of an aidehyde-with 2 mols of a dithiocarbamic acid. The reaction follows probably the following scheme:

rising a mixture of a compound of the probable formula In this case, too, the dithlocarbamic acid may a be replaced by the components necessary for its formation, i. e. by a mixture of an amine and carbon disulflde in equimolecular amounts.

.Amines suitable for carrying out the processes described are, for ihstancadimethylamine, di-

ethyla'mine, di-n-propylamine, methylethylamine, methylcycohexylamine, methyldodecylamine, piperidine, morpholine, monomethylamine, monoethylamine, monocyclohexylamine or benzylamine. I

Suitable aldehydes are, for instance, formaldehyde, acetaldehyde, propionaldehyde' or butyraldehyde.

in which It stands for an alkyl radical and R1 for a radical selected from the group consisting of.the hydrogen atom and an aliphatic residue,

a product-which is obtainable by reacting 1 mol of an aliphaticprimary amine with two mols of an aliphatic aldehyde and two mols of an all phatic dithiocarbamic acid, and an inert diluent;

As dithiocarbamic acids there may be cited by way of example: acid, dimethyl-dithiocarbamic acid, methylcyclohexyl-dithiocarbamicacid, monobenzyl-dithiocarbamic acid, piperldyl-dithiocarbamic acid or morpholyl-dithiocarbamic acidJ The following examplesillustrate the invention without,.however, restricting it thereto:

Example 1 A mixture is prepared'containing 20% of the compound obtained byreacting 1 mol of methylamine, 2 111015 of formaldehyde and 2 mols of t dlmethyldithiocarbamlc acid (the compound melting at 75.5 C. and 80% of fillingand'wetting agents. This'preparation is successfully used in orchardingas spray against fusicladium ina dilution of 1 per cent.

In a 0.5% dilution the said preparation is effective in viniculture against peronospora.

Example 2 A dry seed grain disinfectant is prepared by admixing 20 parts by weight of the compound referred to in Example 1 with 80 parts by weight of talc. In order to effectively combat fusarium of rye this preparation is applied in a quantity of -2-3 parts:1000 parts of seed grain.

Example 3 The compound obtainable by reaction of 1 mol of dimethylamine-1mm of formaldehyde and 1 mol of dimethyldithiocarbamic acid or of 2 mols of dimethylamine, 1 molof formaldehyde and 2 mols of CS: (the compound melding at 42 C.) is dissolvedin water to 1 per cent. Tissues which have been treated with this solution are fast to moldy stains.

The above compound stops the growth of coniophora in a concentration of 0.06% and of fusicladium in a concentration of 0.004%.

Example 4 monomethyl-dithiocarbamic formaldehyde and 2 mols, of a dialkyl-dithiocar 2. Insecticidal and fungicidal preparation comprising a mixture of a compound of the probable formula enrol-nut) R,-N v

' parka-rim).

wherein R stands for an aliphatic radical, 'a

product which is .obtainable by reacting 1 mol of a primary aliphaticamine with 2 mols of ,bamic acid, and an inert diluent.

3. Insecticidal 'and fungicidal preparation comprising a mixture of a compound .of the probable formula wherein R stands for an allqrl radical comprising from 1 to 4 carbon atoms, a product which is obtainable by reacting 1 mol of a primary alkyl amine comprising from 1 to 4' carbon. atoms with 2 mols of formaldehyde and 2 mols of a' dialkyl-dithiocarbamic acid comprising from 1 to 4 carbon atoms in the alkyl group, and an inert diluent.

4. Insecticidal and fungicidal preparation comprising a mixture of a compound of the probable formula melting at 75.5 0., a product which is obtainable by reacting 1 mol of dimethylamine with 2 mols of formaldehyde and 2 mols of dimethyldithiocarbamic acid, and an inert diluent.

5. A compound of the formula wherein R stands for an aliphatic radical, a product which is obtainable by reacting 1 mol of a primary aliphatic amine with 2 mols of formaldehyde and 2 mols of a dialkyl-dithiocarbami acid.

l 6. A compound or the probable formula s om-s- -mormi CHx-N om-s-c-mcm melting at 755 0., a product which is obtainable by reacting 1 mol of dimethylamine with 2 mols of formaldehyde and 2 mols of dimethyldithiocarbamic acid. g

8. Insecticidal and fungicidal preparation comprising a mixture of .a compound of the probable formula R; S ma n RN wherein Y is selected from the class consisting aaamao and v e R is an aliphatic radical linked by one carbon atom to the nitrogen atom, R2 represents the atoms necessary to complete a heterocyclic nitroge'nous" ring system, R1 is aradical selected from the group consisting of the hydrogen atom and an aliphatic radical, a product which is obtainable by reacting 1 mol of a primary aliphatic amine with 2 mols of an aliphatic aldehyde and 2 mols of an aliphatic dithiocarbamic acid, and an inert diluent. I

9. A compound 01' the probable formula Rt fi I dH-s-o-Y ?.N\

on-s-o-y whe ein Y is selected from the class consisting oi.

and h R is an aliphatic radical linked by one carbon atom to the nitrogen atom, R2 represents the atoms necessary to complete a heterooyclic nitrogenous'ring system, R1 is a radical selected from the group consisting of the hydrogen atom and an aliphatic radical, a product which is obtainable by reacting 1 mol of a primary aliphatic amine with 2 mols of an aliphatic aldehyde and 2 mols of an aliphatic dithiocarbamic acid.

EWALD URBSCHAT. FRANZ I-IECKMANNS. 

